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Iron sulfide scaling can pose a significant threat to flow assurance, especially in sour production systems that yields hydrogen sulfide (H2S). When compared to conventional carbonate and sulfate scales, iron sulfide is difficult to inhibit and various risks (liberation of H2S) are associated with chemical removal. Moreover, efficacy of chemical treatment is poor and often uneconomical; and there is currently no true nucleation inhibitor of iron sulfide identified. A strictly anoxic static bottle test setup was developed and various traditional scale inhibitors, such as phosphonates, carboxylic acid polymers, as well as new chemistries were screened for iron sulfide nucleation and growth inhibition. Different concentrations of scaling ions (Fe+2 and S2-) were used to mimic the field to field variation in brine composition. The resulting aqueous phases as well as iron sulfide solid products were characterized using various analytical tools including ICP-OES, particle size analyser and Turbiscan. As expected, conventional scale inhibitors did not show any inhibitory or dispersive effect towards Iron sulfide under tested laboratory conditions. However, a chemistry is identified which can prevent iron sulfide scale deposition at threshold quantities. Specifically, this novel chemistry showed partial iron sulfide nucleation inhibition at early stages and growth inhibition (as high as two orders of magnitude) later. This significant growth inhibition of iron sulfide resulted in excellent dispersion formation that prevents iron sulfide particle aggregation/deposition. Various studies were conducted to understand the chemical-iron sulfide particles interaction and mechanistic aspect of chemical-iron sulfide interaction is identified and discussed. Currently inhibitor packages are being developed for field trials and results will be the subject of future publications. Efficient mitigation of iron sulfide scaling problem has huge industrial and economic importance in oil and gas production. Based on our current laboratory results, it is anticipated that this chemistry will provide a novel chemical treatment option for iron sulfide scaling control at threshold level whereas orders of magnitude more of conventional scale inhibitors may be required. In addition, this novel chemistry also showed promising outcomes on oil-water partitioning test by making finely dispersed iron sulfide particles water-wet thereby preventing the formation of iron sulfide-crude oil emulsion/pad.

This paper highlights efforts taken in answering the following question: "Can horizontal unconventional shale wells be successfully squeezed for scale control?". The Bakken shale formations in North Dakota, Montana and Alberta have presented unique operational challenges during the unconventional play boom. Despite the ability to control scale formation with conventional scale inhibitors under Bakken conditions, scale formation (primarily calcium carbonate) can still remain an operational challenge due to well design and sub-optimal scale inhibitor deployment. Due to limited experience in the industry in scale squeezing fractured long reach horizontal wells, scale squeezes have not been frequently applied in the Bakken. As a result of sub-optimal scale control despite application of suitable scale inhibitors, an in-depth evaluation of scale squeeze chemistries, application methods and scale squeeze modeling has been ongoing in the Bakken. These successful applications are being studied to improve current scale squeeze modeling approaches for horizontal, fracked wells in addition to understanding the factors that impact Bakken scale squeezes. The lessons learned in modeling, application and monitoring of the scale squeezes will be discussed in this paper. Squeeze9 and Place-iT™ field history matching indicate the primary impact to squeeze life is the amount of scale inhibitor (both concentration and volume) used while overflush volumes have less of an impact. This varies from traditional scale squeezes that combine scale inhibitor and overflush volumes to achieve the desired scale squeeze lifetime. Due to the unique brine chemistry of the Bakken, squeeze monitoring has relied less upon traditional ion tracking and almost exclusively upon more advanced environmental scanning electron microscopy (ESEM) of suspended solids within the produced brine samples. Examples of successful Bakken squeezes lasting more than 1 year will be highlighted. The successful applications of scale squeezes in the Bakken are bringing a new method of efficient, cost effective, long term scale control to unconventional plays. The lessons learned in the Bakken, and the resulting advancement of unconventional scale squeeze models and theories, have implications for the global industry as unconventional plays across the world are identified, explored and produced.

It has been proven that scale squeezes can be conducted effectively in the unconventional, horizontal fractured wells in the shale reservoir of the Bakken when using an optimal scale squeeze chemistry. Previous work has discussed inhibitor selection and performance testing along with early case histories and modeling work. This paper discusses new case histories and Place-iT modeling results based on several procedural variations including a range of overflush volumes in the squeeze treatment procedure and the inclusion of acid cleanouts. Novel, reduced-volume squeeze designs have successfully protected wells from scale deposition while limiting the direct and indirect costs associated with extra placement water. For unconventional shale wells in the Bakken, where produced water is typically very high in TDS and TSS, fresh water is most commonly used to execute squeezes. Reducing the total water volume reduces the costs of purchasing, transporting and storing fresh water. The amount of time and cost to pump the job is decreased. Less time and money is spent lifting the placement water, and consequently, there is less deferred production. In addition, in unconventional production acid treatments are commonly carried out in isolation to maintain production. In this work, applying acidizing stages at the front of the squeeze procedures, provides a novel "squimulation" process to fractured reservoir scale control treatments. For these unconventional horizontal wells, the use of larger water volumes—either several times full wellbore volume and/or several times daily water production—has not been shown to improve the longevity or cost-effectiveness of squeeze jobs. Contrary to conventional well applications modeled with Darcy flow, it appears diffusion is the more applicable mechanism for scale inhibitor transport in fractured shale wells. This mechanism is consistent with a reduced dependence on water volume deployed in the treatments. The lessons learned from the unconventional horizontal scale squeezes conducted in the Bakken have resulted in enhanced production and cost savings. There are significant implications for the industry as other key unconventional regions in the U.S. and around the world are looking into scale squeezes as an option for scale control.

Accurate and precise analysis of scale inhibitor residuals is important to managing oilfield squeeze treatments. Phosphonate scale inhibitors are effective for the prevention and control of scale problems in oilfields. The traditional analytical technique for monitoring phosphonate scale inhibitor residuals is inductively coupled plasma optical emission spectroscopy (ICP-EOS). ICP-OES is simple and has been used for monitoring squeeze treatments for decades. However, it can only measure the total phosphorus in the system and is unable to differentiate the different forms of phosphonates in commingled samples. This paper presents a novel technique using ion chromatography and mass spectrometry (IC-MS and IC-MS/MS) for monitoring and quantifying different phosphonate scale inhibitors with high sensitivity and specificity. Ion chromatography efficiently separates phosphonate ions from other salt ions, and mass spectrometry speciates and quantitates molecular ions or fragment ions of each phosphonate. Previous work in our group (Zhang, et.al., 2014) had shown that IC-MS could be used to differentiate two phosphonates in a squeeze treatment using the characteristic molecular ions of each phosphonate. As the complexity of the squeeze treatment increases with the addition of other phosophates to the local oilfield, the development of an advanced IC-MS/MS method has been required to differentiate up to four phosphonates in a single commingled sample. This innovative technique has a detection limit of <1 ppm for each phosphonate in the mixture. The technique has been validated using both synthetic brine and field brine. Solid phase extraction cleanup work has also been performed to improve the capability of the technique in high-salinity brines. This novel analytical method will provide a powerful tool in squeeze scale management for subsea and deepwater oilfields.